CN105619979A - Method for manufacturing heat resistance adhesive sheet and function film - Google Patents

Method for manufacturing heat resistance adhesive sheet and function film Download PDF

Info

Publication number
CN105619979A
CN105619979A CN201510810393.7A CN201510810393A CN105619979A CN 105619979 A CN105619979 A CN 105619979A CN 201510810393 A CN201510810393 A CN 201510810393A CN 105619979 A CN105619979 A CN 105619979A
Authority
CN
China
Prior art keywords
film
thermostability
bonding sheet
methyl
resin bed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510810393.7A
Other languages
Chinese (zh)
Other versions
CN105619979B (en
Inventor
高桥亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lintec Corp
Original Assignee
Lintec Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lintec Corp filed Critical Lintec Corp
Publication of CN105619979A publication Critical patent/CN105619979A/en
Application granted granted Critical
Publication of CN105619979B publication Critical patent/CN105619979B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

The invention provides a method for manufacturing a heat resistance adhesive sheet and a function film capable of reducing the manufacture cost of the function film by decreasing manufacture processes. The heat resistance adhesive sheet (1) comprises a stripping film (10), an adhesive layer (14), and a base material film (21). The stripping film (10) comprises a stripping base material (11) formed by a polyester film, a resin layer (12) disposed on a main surface of the stripping base material (11), a stripper layer (13) disposed on the other main surface of the stripping base material (11). The adhesive layer (14) is arranged on the stripper layer (13). The base material film (21) is arranged on the adhesive layer (14). The absolute value [delta] haze value of a difference between the initial haze value of the stripping film (10) and the heated haze value of the stripping film (10) heated for two hours at the temperature 150 degrees centigrade is below 0.15%.

Description

The manufacture method of thermostability bonding sheet and functional membrane
Technical field
The present invention relates to the manufacture method of thermostability bonding sheet and the functional membrane with functional layer, in particular to the manufacture method of the thermostability bonding sheet using polyester film as peeling base and functional membrane.
Background technology
In the past, in the manufacturing process of touch panel, employ the nesa coating possessing the transparent electrode layers such as ITO (IndiumTinOxide) film. This nesa coating is made by being respectively provided with hard conating on a pair interarea of supporter, arranges transparent electrode layer on a hard conating, the bonding sheet simultaneously strippingly fitted as surface protection film on another hard conating. The bonding sheet used during as the manufacture of nesa coating, it is proposed that be provided with the bonding sheet (for example, referring to patent documentation 1) of adhesive phase on the base material film formed by the polyester film with thermostability.
It addition, in the manufacturing process of touch panel, nesa coating is pasted on glass substrate etc. by optics bonding film (OpticalClearAdhesive, hereinafter sometimes referred to " OCA "). The stripping film generally formed by polyester film at the two sides lamination of OCA.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-205567 publication
Summary of the invention
The problem that invention to solve
But; in the manufacturing process of nesa coating, it is provided with another surface mount of nesa coating (or raw material film of nesa coating) of transparency conducting layer on a surface to have the peeling base bonding sheet as the protecting film of transparency conducting layer of adhesive phase. And, implement the annealing that nesa coating is heated when having pasted bonding sheet after, remove the peeling base of bonding sheet, nesa coating is pasted onto on glass substrate etc. across adhesive phase, is consequently for the products such as touch panel. As mentioned above, in the manufacturing process of existing nesa coating, the bonding sheet being heat treatment together with transparency conducting layer needs thermostability, and simultaneously need to bonding sheet is pasted on the operation of the rear side of the transparency conducting layer of nesa coating, there is the situation that manufacturing process is complicated.
The present invention carries out in view of above-mentioned practical situation, its object is to provide a kind of excellent heat resistance and simultaneously because manufacturing process shortens and can reduce the thermostability bonding sheet of the manufacturing cost of functional membrane and the manufacture method of functional membrane.
The method solving problem
The thermostability bonding sheet of the present invention possesses stripping film, adhesive phase and base material film, described stripping film comprises the peeling base formed by polyester film, be arranged on an interarea of described peeling base resin bed and be arranged at the peeling agent layer on another interarea of described peeling base, described adhesive phase is arranged on described peeling agent layer, described base material film is arranged on described adhesive phase, it is characterized in that, the initial stage haze value of described stripping film is with to heat the absolute value delta haze value of the difference of haze value after the heating after 2 hours at 150 DEG C be less than 0.15%.
According to this composition, owing to before and after heating, the rate of change of the haze value of stripping film is less, therefore, it is possible to realize the thermostability bonding sheet of excellent heat resistance. Further, since the stripping film comprising peeling base, resin bed and peeling agent layer can be utilized to protect the rear side of the functional layer on base material film, the operation of the screening glass pasting defencive function layer rear side therefore can be omitted when manufacturing functional membrane. It is thereby achieved that the thermostability bonding sheet of the manufacturing cost of functional membrane can be reduced by shortening manufacturing process.
For the thermostability bonding sheet of the present invention, it is preferable that described peeling agent layer is formed by the solidification of addition reaction-type polysiloxanes.
In the thermostability bonding sheet of the present invention, it is preferable that described resin bed is formed to solidify by compositions by the resin bed containing (A) bisphenol A type epoxy compound, (B) petchem and (C) multifunctional amino-compound and forms. According to this composition, resin bed is set on a surface of peeling base owing to the resin bed formation compositions containing bisphenol A type epoxy resin compound, petchem and multifunctional amino-compound being solidified, therefore makes the crosslink density of resin bed in the scope of appropriateness. Thus, thermostability bonding sheet can not only prevent oligomer from precipitateing into the face side of thermostability bonding sheet from polyester film, even and if thermostability bonding sheet is applied pressure, impacts and be also possible to prevent resin bed and rupture, it is possible to prevent oligomer from spilling from breaking part.
In the thermostability bonding sheet of the present invention, for described resin bed formation compositions, it is preferable that the content of described bisphenol A type epoxy compound is the content of more than 50 mass % and below 80 mass %, described petchem be the content of more than 5 mass % and below 30 mass %, described multifunctional amino-compound is more than 10 mass % and below 40 mass %.
In the thermostability bonding sheet of the present invention, it is preferable that the weight average molecular weight of described biphenol type epoxy compound is more than 10000 and less than 50000.
In the thermostability bonding sheet of the present invention, it is preferable that the glass transition temperature (Tg) of described petchem is more than 0 DEG C and less than 50 DEG C.
In the thermostability bonding sheet of the present invention, it is preferable that described resin bed is that the coating layer being coated on described base material film to be formed the solution of described resin bed formation compositions is heated and the cured film that formed.
In the thermostability bonding sheet of the present invention, it is preferable that the thickness of described resin bed is more than 50nm and below 500nm.
The manufacture method of the functional membrane of the present invention includes: lamination procedure, film formation process and heat treatment step,
Described lamination procedure includes: adhesive phase and described base material film described in lamination successively comprising the peeling base formed by polyester film, on the described peeling agent layer of the stripping film of the resin bed that is arranged on an interarea of described peeling base and the peeling agent layer that is arranged on another interarea of described peeling base, thus the thermostability bonding sheet that absolute value delta haze value is less than 0.15% of the difference of haze value after heating after obtaining the initial haze value of described stripping film and heating 2 hours at 150 DEG C
Described film formation process includes: using conductive material film forming as functional layer on the described base material film of described thermostability bonding sheet,
Described heat treatment step includes: to film forming, the described thermostability bonding sheet of described functional layer is heated processing.
According to the method; owing to the rear side of the stripping film comprising peeling base, resin bed and the peeling agent layer functional layer to being arranged on base material film can be utilized to be protected by; therefore when manufacturing functional membrane, it is convenient to omit paste the operation of the screening glass of defencive function layer rear side. Thus, it is possible to realize to be reduced the thermostability bonding sheet of the manufacturing cost of functional membrane by shortening manufacturing process.
In the manufacture method of the functional membrane of the present invention, it is preferable that described functional layer is transparency conducting layer.
The effect of invention
In accordance with the invention it is possible to provide a kind of excellent heat resistance and the thermostability bonding sheet of the manufacturing cost of functional membrane and the manufacture method of functional membrane can be reduced by shortening manufacturing process.
Accompanying drawing explanation
Fig. 1 is the schematic cross sectional view of the thermostability bonding sheet of an embodiment of the invention.
Fig. 2 is the generalized section of the laminated body of an embodiment of the invention.
Fig. 3 is the schematic cross sectional view of another example of the thermostability bonding sheet illustrating an embodiment of the invention.
Fig. 4 A is the explanation figure of the manufacture method of the functional membrane of embodiments of the present invention.
Fig. 4 B is the explanation figure of the manufacture method of the functional membrane of embodiments of the present invention.
Fig. 4 C is the explanation figure of the manufacture method of the functional membrane of embodiments of the present invention.
Symbol description
1,2 thermostability bonding sheet
3 laminated body
10 stripping films
11 peeling base
12 resin beds
13 peeling agent layers
14 adhesive phases
141 cores
142 the 1st adhesive phases
143 the 2nd adhesive phases
21 base material films
22 functional layers
Detailed description of the invention
Hereinafter, with reference to accompanying drawing, an embodiment of the invention is described in detail. It should be noted that the present invention is not limited to following embodiment, it is possible to implement after suitably changing. It addition, give identical symbol to avoid repeat specification to following embodiment is commonly constructed key element.
Fig. 1 is the schematic cross sectional view of the thermostability bonding sheet 1 of an embodiment of the invention. As shown in Figure 1, the thermostability bonding sheet 1 of present embodiment possesses stripping film 10, described stripping film 10 have formed by polyester film peeling base 11, be arranged on an interarea of peeling base 11 and make resin bed formed with compositions solidify resin bed 12 and be arranged on another interarea of peeling base 11 and make peeling agent layer formed with compositions solidify peeling agent layer 13. On the peeling agent layer 13 of stripping film 10, there is base material film 21 across adhesive phase 14 lamination. That is, in this thermostability bonding sheet 1, lamination has resin bed 12, peeling base 11, peeling agent layer 13, adhesive phase 14 and base material film 21 successively.
Base material film 21 is provided with (with reference to Fig. 2) such as transparency conducting layers as functional layer 22. For the thermostability bonding sheet 1 of present embodiment, it is possible to be in that on base material film 21 to make transparent conductive material film forming and functional layer 22 is set to after forming laminated body 3, with the state of laminated body 3 through utilizing the annealing of heating to form transparency conducting layer. It should be noted that as functional layer 22, it is possible to enumerate such as transparency conducting layer, but be not limited to this.
The thermostability bonding sheet 1 of present embodiment can be rolled into a roll to carry out keeping on core. For this bonding sheet 1, for instance, it is possible to from the heat treated that the state uncoiling being rolled into a roll enforcement are given, then remove stripping film 10, the face exposed of adhesive phase 14 is pasted on and is attached on thing, be consequently for the manufacture of various product. As being attached thing, it is possible to enumerate such as glass substrate. As given heat treated, it is possible to implement various heat treated in the scope playing effect of the present invention, for instance the annealing of the crystallization for transparent conductive material can be enumerated.
For the thermostability bonding sheet 1 of present embodiment, for instance, by make above-mentioned as the transparent conductive material film forming of functional layer 22 after be heated and be annealed processing, it is possible to for manufacturing the nesa coating used in touch panel etc. In this thermostability bonding sheet 1, the �� haze value of stripping film 10 is less than 0.15%, described �� haze value be initial stage haze value with heat 2 hours at 150 DEG C after heating after the absolute value of difference of haze value. Thus, even be provided as the transparency conducting layer of functional layer 22 on thermostability bonding sheet 1 and implement the annealing utilizing heating, the change of the haze value of the stripping film before and after annealing is also sufficiently small, therefore, it is possible to directly implement annealing when the thermostability bonding sheet 1 being provided with transparency conducting layer possesses adhesive phase 14. Additionally; rear side (the one side side of thermostability bonding sheet 1) in functional layer 22 is provided with stripping film 10 across adhesive layer 14; therefore stripping film 10 can also play in prior art the effect of the screening glass being pasted onto the nesa coating back side such that it is able to reduces cost because of the shortening of the manufacturing process of nesa coating. Additionally, rear side in functional layer 22 has and is formed, by the resin bed given, the resin bed 12 being arranged to by compositions, therefore, it is possible to prevent oligomer from precipitating out to the one side side of thermostability bonding sheet 4, even when being rolled into a roll on core with the state of functional layer 22 film forming, although employing polyester film as peeling base 11, remain able to prevent surface contamination and the damage of functional layer 22.
Fig. 3 is the generalized section of other configuration example of the thermostability bonding sheet 1 illustrating present embodiment. As shown in Figure 3, in this thermostability bonding sheet 2, the adhesive phase 14 of thermostability bonding sheet 2 comprises core 141, the 1st adhesive phase 142 that is arranged on a surface of this core 141 and the 2nd adhesive phase 143 being arranged on another surface of core 141. As core 141, it is possible to use various films, paper and non-woven fabrics etc. such as such as identical with peeling base 11 polyester films. 1st adhesive phase 142 can be made up of the material identical with adhesive phase 14 with the 2nd adhesive phase 143. Constitute as described above, it is possible to obtain the effect identical with the thermostability bonding sheet 1 shown in above-mentioned Fig. 1. Hereinafter, the various elements of the thermostability bonding sheet 1,2 constituting present embodiment are illustrated.
(peeling base 11)
As peeling base 11, it is possible to use various polyester films. The excellent heat resistance of polyester film, even if be at high temperature annealed transparent electrode layers such as nesa coatings processing, without the unfavorable condition such as shrinking and melted. As polyester film, it is preferable that the such as polyester film such as polyethylene terephthalate, polybutylene terephthalate (PBT) and PEN. It addition, as polyester film, more preferably biaxial tension polyethylene terephthalate film.
The thickness of peeling base 11 suitably can change according to purposes. From the viewpoint of keep the viewpoint of thermostability bonding sheet intensity and guarantee flexibility when manufacturing nesa coating etc. by roll-to-roll (rolltoroll) mode, the thickness of peeling base 11 is preferably more than 10 ��m, is more preferably more than 20 ��m, more preferably more than 30 ��m, and be preferably less than 250 ��m, be more preferably less than 225 ��m, more preferably less than 200 ��m. If it is considered that case above, then the thickness of peeling base 11 is preferably more than 10 ��m and less than 250 ��m, more preferably more than 20 ��m and less than 225 ��m, more preferably more than 30 ��m less than 200 ��m.
(resin bed 12)
From the viewpoint of prevent oligomer from precipitating out from peeling base 11, resin bed 12 be preferably by contain (A) bisphenol A type epoxy compound (hereinafter also referred to as " (A) composition "), (B) petchem (hereinafter also referred to as " (B) composition "), (C) multifunctional amino-compound (hereinafter also referred to as " (C) composition ") resin bed form the cured film with compositions solidification. Hereinafter, each composition constituting resin bed formation compositions is described in detail.
< (A) bisphenol A type epoxy compound >
As (A) bisphenol A type epoxy compound, it is possible to enumerate such as bisphenol A type epoxy resin etc., described bisphenol A type epoxy resin is the copolymer that bisphenol-A is formed with epoxychloropropane.
From the viewpoint of the cured film of appropriately crosslinked density can be obtained, it is preferable that the weight average molecular weight (Mw) of (A) composition is more than 10000 and less than 50000. If (A) weight average molecular weight (Mw) of composition is more than 10000, then can obtain enough crosslink densities as cured film, it is possible to be substantially prevented from the precipitation of oligomer. If it addition, the weight average molecular weight (Mw) of (A) composition is less than 50000, then cured film can be given the flexibility of appropriateness, it is possible to prevent the fracture of resin bed 12 when making thermostability bonding sheet 1 deform.
Gross mass relative to resin bed formation compositions, in resin bed formation compositions, the use level of (A) composition is preferably more than 50 mass %, it is more preferably more than 60 mass %, and is preferably below 80 mass %, more preferably below 70 mass %.
< (B) petchem >
As (B) petchem, known various petchem can be used in the scope that can play effect of the present invention. As petchem, it is possible to enumerate the resin such as obtained by condensation reaction by polyhydric alcohol and polyprotic acid. As such resin, it is possible to enumerate: the condensation substance of binary acid and dihydroxylic alcohols or the nonconvertible petchem by non-drying oil fatty acid etc., condensation substance being modified and obtaining and the transformant petchem etc. of condensation substance formed as alcohol more than binary acid and ternary. Petchem can be used alone one, it is also possible to combination uses two or more.
As polyhydric alcohol, can enumerate such as: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1, ammediol, 1, the dihydroxylic alcohols such as 4-butanediol and neopentyl glycol, the trihydroxylic alcohols such as glycerol, trimethylolethane and trimethylolpropane, the polyhydric alcohol more than quaternary such as diglycerol, two triglycerols, tetramethylolmethane, dipentaerythritol, mannitol and Sorbitol. These polyhydric alcohol can be used alone one, it is also possible to combination uses two or more.
As polyprotic acid, can enumerate such as: the aromatic polyvalent acid such as phthalic anhydride, p-phthalic acid, M-phthalic acid and trimellitic anhydride, the aliphatic saturated polybasic acids such as succinic acid, adipic acid and decanedioic acid, the unsaturated polyprotic acid of aliphatic such as maleic acid, maleic anhydride, fumaric acid, itaconic acid and citraconic anhydride, the polyprotic acid etc. that cyclopentadiene-maleic anhydride adduct, terpenes-maleic anhydride adduct and rosin-maleic acid anhydride addition product etc. are obtained by Diels-Alder reaction (Diels-Alderreaction). These polyprotic acid can be used alone one, it is also possible to combination uses two or more.
As (B) petchem, it is preferable that there is the compound of the active hydrogen of the hydroxyl of the reaction site becoming cross-linking reaction, carboxyl and amino etc., more preferably there is hydroxyl. Preferably the hydroxyl value of (B) petchem is more than 5mgKOH/g, is more preferably more than 10mgKOH/g, and is preferably below 500mgKOH/g, is more preferably below 300mgKOH/g.
From the viewpoint of resin bed 12 can be given appropriateness flexibility, it is preferable that the number-average molecular weight (Mn) of (B) petchem is more than 500, is more preferably more than 1000, and is preferably less than 10000, is more preferably less than 5000. From the viewpoint of resin bed 12 can be given appropriateness flexibility, it is preferable that the glass transition temperature Tg of petchem (B) is more than 0 DEG C, is more preferably more than 10 DEG C, and is preferably less than 50 DEG C, is more preferably less than 40 DEG C. By using such petchem (B), the cured film of resin bed 12 can be given the flexibility of appropriateness, even if thermostability bonding sheet 1 is under pressure, impacts, it is also possible to prevent the fracture of resin bed 12, such that it is able to prevent the oligomer caused by fracture from spilling.
Relative to (A) composition 100 mass parts, in resin bed formation compositions, the use level of (B) composition is preferably more than 5 mass parts, is more preferably more than 10 mass parts, and is preferably below 50 mass parts, is more preferably below 45 mass parts.
Gross mass relative to resin bed formation compositions, in resin bed formation compositions, the use level of (B) composition is preferably more than 5 mass %, it is more preferably more than 10 mass %, and is preferably below 30 mass %, more preferably below 20 mass %.
The multifunctional amino-compound > of < (C)
As (C) multifunctional amino-compound, can enumerate such as: the melamine compounds such as HMMM, methylated melamine compound and butylated melamines compound, the carbamide compounds such as methyl urea compounds and Butylurea compound, methylate the benzoguanamine compound such as benzoguanamine resin and butylation benzoguanamine compound, ethylenediamine, 1,4-butanediamine, 1,6-hexamethylene diamine, N, N '-the Diamines such as diphenyl ethylene diamine and p dimethylamine etc. Wherein, from the viewpoint of curable, it is preferable that HMMM.
Relative to (A) composition 100 mass parts, in resin bed formation compositions, the use level of (C) composition is preferably more than 20 mass parts, is more preferably more than 25 mass parts, and it is preferably below 60 mass parts, more preferably below 55 mass parts.
Gross mass relative to resin bed formation compositions, in resin bed formation compositions, the use level of (C) composition is preferably more than 10 mass %, it is more preferably more than 20 mass %, and is preferably below 40 mass %, more preferably below 30 mass %.
< (D) acidic catalyst >
In order to promote curing reaction, as resin bed formation compositions, it is possible to use the resin combination containing the known acidic catalyst such as hydrochloric acid, p-methyl benzenesulfonic acid (D) (hereinafter also referred to as " (D) composition ") as required. When coordinating (D) composition, relative to the gross mass of resin bed formation compositions, it is preferable that the content of (D) composition is more than 1 mass % and below 5 mass %.
Resin bed 12 can be obtained as below: above-mentioned resin bed formation compositions organic solvent dissolution is obtained solution, this solution is coated on peeling base 11 forms coating layer, then make the coating layer formed more than 100 DEG C and be heating and curing under 170 DEG C of temperature below more than 5 seconds and less than 5 minutes. Coating method as resin bed formation compositions, it is possible to enumerate such as: gravure coating process, stick coating method, spraying process, spin-coating method, air knife coating method, rolling method, scraper plate rubbing method, door roller rubbing method and die coating method etc. Wherein, it is preferable that gravure coating process and stick coating method, more preferably stick coating method. It addition, as the heating/drying means of resin bed formation compositions, it is possible to enumerate and such as use hot-air drying stove etc. to carry out the method etc. of heated drying.
As organic solvent, as long as can the solvent of dissolving resin layer formation compositions, it does not have limit especially. As organic solvent, can enumerate such as: the aromatic series kind solvents such as benzene, toluene and dimethylbenzene, the aliphatic solvent such as normal hexane and normal heptane, the esters solvent such as ethyl acetate and butyl acetate, the ketones solvents such as butanone, methyl iso-butyl ketone (MIBK), Ketohexamethylene and Ketocyclopentane, the alcohols solvent such as isopropanol and methanol etc.
From the viewpoint of effectively suppress oligomer to precipitate out, the thickness of resin bed 12 is preferably more than 50nm, is more preferably more than 80nm, more preferably more than 100nm, and is preferably below 500nm, is more preferably below 300nm, more preferably below 250nm. When the thickness of resin bed 12 is more than 50nm, oligomer can be fully suppressed to precipitate out, when the thickness of resin bed 12 is below 500nm, it is possible to when preventing in peeling base 11 coating to form resin bed 12 along with the crosslinking of resin bed 12 curling caused by cure shrinkage. Considering case above, the thickness of resin bed 12 is preferably more than 50nm and below 500nm, more preferably more than 80nm and below 300nm, more preferably more than 100nm and below 250nm.
(peeling agent layer 13)
Peeling agent layer 13 such as can be formed by the peeling agent layer comprising releasing agent and be formed with the solidfied material of compositions. As peeling agent layer formation compositions, as long as peeling agent layer 13 can be given the adhesive phase 14 being stacked on peeling agent layer 13 from the function peeled off stripping film 10, it does not have limit especially. As releasing agent, it is possible to enumerate such as: polyorganosiloxane resin, chain alkyl resin and alkyd resin etc.
As polysiloxane-based releasing agent, it is possible to enumerate addition reaction-type polysiloxanes, condensation reaction type polysiloxanes, energy-line solidifying type polysiloxanes. It addition, in order to adjust peeling force, it is possible to use without the polydimethylsiloxane of functional group, phenyl modified polysiloxanes, polyorganosiloxane resin, silicon dioxide, cellulose compound as additive.
The thickness of peeling agent layer 13 is preferably more than 30nm, is more preferably more than 50nm, more preferably more than 70nm, and is preferably below 500nm, is more preferably below 400nm, more preferably below 300nm. If the thickness of peeling agent layer 13 is in such scope, then easily between stripping film 10 and adhesive phase 14, obtains uniform demolding performace, and be possible to prevent between the face of the stripping film 10 contacted when stripping film 10 is rolled into a roll and stick to each other.
Peeling agent layer 13 such as can be formed: utilizes existing known coating method peeling agent layer formation compositions to be coated on a face of peeling base 11, then heats at a given temperature, dries and makes it solidify. At this, it is also possible to the solution after peeling agent layer formation compositions being diluted with organic solvent is coated in peeling base 11. As organic solvent, it is possible to enumerate: the aromatic hydrocarbon such as toluene and dimethylbenzene, the fatty acid ester such as ethyl acetate and butyl acetate, the ketone such as butanone and methyl iso-butyl ketone (MIBK), the aliphatic hydrocarbon such as hexane and heptane etc.
Coating method as peeling agent layer formation compositions, it is possible to enumerate such as: gravure coating process, stick coating method, spraying process, spin-coating method, air knife coating method, rolling method, scraper plate rubbing method, door roller rubbing method and die coating method etc. Wherein, it is preferable that gravure coating process and stick coating method, more preferably stick coating method. It addition, as the heating/drying means of peeling agent layer formation compositions, it is possible to enumerate and such as use hot-air drying stove etc. to carry out the method etc. of heated drying. Baking temperature is such as more than 50 DEG C and less than 150 DEG C. It addition, drying time is preferably such as 10 seconds��5 minutes.
(stripping film 10)
Stripping film 10 is made up of above-mentioned resin bed 12, peeling base 11 and peeling agent layer 13 lamination successively. Thickness as stripping film 10, for instance be preferably more than 10 ��m, more preferably more than 15 ��m, and it is preferably less than 200 ��m, more preferably less than 100 ��m.
(adhesive phase 14)
For the thermostability bonding sheet 1 of present embodiment, it is heated when adhesive phase 14 is sandwiched between peeling base 11 and base material film 21 processing. In this heat treated, the binding agent constituting adhesive phase 14 is exposed to high temperature, therefore when using the relatively low common binding agent of thermostability, it some times happens that the decrease in viscosity of binding agent and make the phenomenon that adhesive phase 14 exposes from the end of base material film 21 and stripping film 10. The binding agent of the adhesive phase 14 exposed from the end of base material film 21 and stripping film 10 sometimes shifts to adhere to and pollutes the article (surface contamination such as, caused by being transferred to the transport roller and thermostability bonding sheet that make annealing treatment device again) contacted the object of contact.
Therefore, in the present embodiment, from improving the viewpoint of the adhesive phase 14 thermostability when heat treated and making the better viewpoint of adhesion durability consider, the preferred adhesive phase 14 storage modulus (G) when 23 DEG C is more than 0.3MPa, it is more preferably 0.35MPa, and it is preferably below 50MPa, more preferably below 15MPa, more preferably below 12MPa. It should be noted that in the present embodiment, storage modulus (G) is to make the thick cylindric test film of 8mm �� �� 3mm by the adhesive laminate of thickness 30 ��m, measures, by reversing cutback technique, the value obtained under the following conditions.
Determinator: Measurement of Dynamic Viscoelasticity device (model: DYNAMICANALYZERRDAII, RHEOMETRICS company manufactures)
Frequency: 1Hz
Temperature: 23 DEG C, 80 DEG C
It addition, from the viewpoint of the viewpoint of the thermostability of adhesive phase 14, durability and stability and prevent the binding agent pollution to being attached thing, it is preferable that the gel fraction of adhesive phase 14 is more than 85%, more preferably more than 90 and less than 99.9%.
Adhesive phase 14 can use the known adhesive compositions such as acrylic adhesives, natural rubber based binder, synthetic rubber class binding agent, polyethers binding agent, polyester adhesive, polyurethane binding and urethane acrylate class binding agent to be formed. As acrylic adhesives, it is possible to enumerate the adhesive phase formation compositions such as containing acrylic polymer. Binding agent with form supplies such as solvent-borne type, emulsion-type, hot melt no-solvent type and ultraviolet curing no-solvent types, can utilize and form adhesive phase 14 corresponding to various forms of coating processes.
< acrylic polymer >
Acrylic polymer can by comprise (methyl) acrylate, the monomer polymerization of vinyl monomer and aromatic monomer etc. containing hydroxyl and carboxyl isoreactivity group and obtain.
As (methyl) acrylate, can enumerate such as: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, the just own ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid myristyl ester, (methyl) alkyl acrylate that atomic number of alkyl carbon is more than 1 and less than 20 of the ester moieties such as (methyl) aliphatic acrylate and (methyl) octadecyl acrylate. here, " (methyl) acrylic acid " expression " acrylic acid " or " methacrylic acid ". these acrylic monomers can be used alone one, it is also possible to combination uses two or more.
As the vinyl monomer containing reactive functional groups, it is possible to enumerate such as: (methyl) acrylate of the hydroxyls such as (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate; Carboxylic (methyl) acrylate such as 1,4-bis-(methyl) acryloyl-oxyethyl pyromellitic dianhydride, 4-(methyl) acryloyl-oxyethyl trimellitic anhydride, N-(methyl) acryloyl group para-amino benzoic acid, 2-(methyl) acryloyl-oxy yl benzoic acid, N-(methyl) acryloyl group-5-aminosalicylic acid, acrylic acid, methacrylic acid; (methyl) acrylate containing primary amino radical and secondary amino group such as (methyl) acrylate, (methyl) acrylic acid ethyl amino ethyl ester, (methyl) acrylic-amino propyl ester, (methyl) acrylic acid ethyl amino propyl ester; (methyl) acrylate etc. containing sulfydryl such as methacrylic acid 2-(methyl mercapto) ethyl ester. These monomers can be used alone one, it is also possible to combination uses two or more.
In acrylic polymer, the content coming from the construction unit of the vinyl monomer containing reactive functional groups is preferably 0.01 mole of more than %, is more preferably 0.1 mole of more than %, and is preferably 20 moles of below %, is more preferably 10 moles of below %.
From the viewpoint of improve the refractive index of adhesive phase 14, as aromatic monomer, it is preferable that its homopolymer demonstrates the high refractive index, acrylic monomer of the glass transition temperature of less than 50 DEG C.
As aromatic monomer, can enumerate such as: Phenoxyethyl (methyl) acrylate, 2-(1-naphthoxy)-1-ethyl (methyl) acrylate, 2-(2-naphthoxy)-1-ethyl (methyl) acrylate, 6-(1-naphthoxy)-1-hexyl (methyl) acrylate, 6-(2-naphthoxy)-1-hexyl (methyl) acrylate, 8-(1-naphthoxy)-1-octyl group (methyl) acrylate, 8-(2-naphthoxy)-1-octyl group (methyl) acrylate, 2-thiophenyl-1-ethyl (methyl) acrylate, 6-(4, the bromo-2-isopropyl phenoxy group of 6-bis-)-1-hexyl (methyl) acrylate, 6-(4, the bromo-2-sec-butyl phenoxy group of 6-bis-)-1-hexyl (methyl) acrylate, 2, bromo-4-nonyl phenyl (methyl) acrylate of 6-bis-and 2, 6-bis-bromo-4-dodecylphenyl (methyl) acrylate etc.
As adhesive phase formation compositions, it is preferable that containing the compositions of acrylic compounds triblock copolymer. As acrylic compounds triblock copolymer, it is preferable that the weight average molecular weight (Mw) shown in following formula (1) is more than 50000 and less than 300000, molecular weight distribution (Mw/Mn) is 1.0��1.5, the content of polymer blocks B is more than 50 mass % and the copolymer of below 95 mass %.
A1-B-A2 ... formula (1)
(in formula (1), A1 and A2 separately represents the methacrylate polymer block that glass transition temperature is more than 100 DEG C, and B represents the methacrylate polymer block that glass transition temperature is less than-20 DEG C. )
For the acrylic compounds triblock copolymer shown in above-mentioned formula (1), generally using in the acrylic compounds triblock copolymer forming micro phase separation structure at temperature at binding agent, polymer blocks A1 and A2 works as contained phase (the false crosslinking points of physical property). Thus, even if not carrying out chemical crosslinking can show enough cohesivenesss, thus playing adhesion characteristic and the durability of excellence yet. From durability, thermostability, the anterethic viewpoint of the followability of substrate deformation and the stress of appropriateness is considered, as polymer blocks A1 and the A2 in the acrylic compounds triblock copolymer that above-mentioned formula (1) represents, preferred glass transition temperature is more than 100 DEG C and less than 200 DEG C, more preferably more than 100 DEG C and less than 150 DEG C. It should be noted that, A1 and A2 can be polymer [the mutually the same same methacrylate polymer such as molecular weight, monomer composition, stereochemical structure (degree of syndiotacticity etc.)], can also be additionally different polymer [in molecular weight, monomer composition, stereochemical structure (degree of syndiotacticity etc.) etc. or more than two mutually different methacrylate polymer].
Alkylmethacrylate unit as polymer blocks A1 and A2, it is possible to enumerate such as: the unit formed by alkyl methacrylates such as the just own ester of methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, Tert-butyl Methacrylate, methacrylic acid, cyclohexyl methacrylate, 2-Ethylhexyl Methacrylate, n octyl methacrylate, lauryl methacrylate, Tridecyl methacrylate base ester, octadecyl methacrylate, isobornyl methacrylates. Polymer blocks A1 and A2 can only be formed by a kind of of above-mentioned alkylmethacrylate unit, it is also possible to is formed by two or more. Wherein, from the viewpoint of obtain easiness, durability and weatherability, polymer blocks A1 and A2 is preferably made up of methyl methacrylate units one.
From the viewpoint of the bonding force of adhesive phase 14 and reprocessing property, as polymer blocks B, it is preferable that the glass transition temperature formed by alkyl acrylate is the polymer blocks of less than-20 DEG C. From the viewpoint of the stability under cryogenic conditions, as polymer blocks B, more preferably glass transition temperature is the polymer blocks of less than-30 DEG C, more preferably the polymer blocks of more than-80 DEG C and less than-40 DEG C.
As polymer blocks B, it is possible to enumerate such as: the unit formed by alkyl acrylates such as the just own ester of acrylic acid methyl ester., ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, acrylic acid, cyclohexyl acrylate, 2-EHA, n-octyl, dodecylacrylate, tridecyl acrylate, octadecyl acrylate. Polymer blocks B can only be formed by a kind of aforesaid propylene acid alkyl ester unit, it is also possible to is formed by two or more. Wherein, binding agent bonding force at low temperatures and viscosity is made to become good viewpoint and improve bonding force when peeling off at a high speed and suppress creak squish (zipping) from the viewpoint of make the glass transition temperature of polymer blocks be less than-20 DEG C, as polymer blocks B, it is preferable that one or more of the unit formed by propyl acrylate, n-butyl acrylate, 2-EHA, n-octyl are constituted. Additionally, from the viewpoint of obtain that being separated of easiness and polymer blocks A1, A2 and polymer blocks B is apparent from, the false crosslinking points of polymer blocks A is destroyed, the higher and excellent in te pins of durability as the cohesiveness of binding agent, polymer blocks B is preferably formed by n-butyl acrylate unit and/or 2-EHA unit.
Polymer blocks A1, A2 and polymer blocks B as the acrylic compounds triblock copolymer shown in above-mentioned formula (1), in the scope playing effect of the present invention, a small amount of (such as, being commonly angled relative to the ratio that quality is below 10 mass % of each polymer blocks) other monomeric unit can also be contained. as other monomeric unit, can enumerate such as: by (methyl) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-amino ethyl ester, (methyl) glycidyl acrylate and (methyl) tetrahydrofurfuryl acrylate etc. have (methyl) acrylate of functional group, (methyl) acrylic acid, .beta.-methylacrylic acid, maleic acid, maleic anhydride, fumaric acid and (methyl) acrylamide etc. have the vinyl monomer of carboxyl, styrene, the aromatic vinyl class monomer such as ��-methyl styrene and p-methylstyrene, butadiene and isoprene equiconjugate diene-based monomer, the olefin monomer such as ethylene and propylene, the unit that the lactone monomer such as 6-caprolactone and valerolactone etc. are formed. these monomeric units can individually contain one, it is also possible to containing two or more.
Polymerization as acrylic polymer, it does not have limit especially, it is possible to be polymerized by common radical polymerization. As radical polymerization, it is possible to enumerate: polymerisation in solution, suspension polymerisation, emulsion polymerization and polymerisation in bulk etc.
From the viewpoint of thermostability, the molecular weight of acrylic polymer is preferably more than 500,000 with Weight-average molecular gauge, more preferably more than 600,000, more preferably more than 700,000. The weight average molecular weight of acrylic polymer is more big, and the entanglement of strand is more many, it is suppressed that flowing during high temperature, and thermostability improves. It addition, from the viewpoint of screening characteristics or with the adaptation being attached thing, the molecular weight of acrylic polymer is preferably less than 2,000,000 with Weight-average molecular gauge, more preferably less than 1,800,000. As long as the upper limit of the weight average molecular weight of acrylic polymer is in above-mentioned scope, just adhesive phase formation compositions excess dilution can be coated, and mobility will not be excessively not enough, adhesive phase can be followed the rough surface being attached thing and be guaranteed adaptation. It should be noted that above-mentioned weight average molecular weight is the value measuring and being converted into polystyrene by gel permeation chromatography (GPC) method.
< active energy ray-curable compound >
It addition, from the viewpoint of improve elastic modelling quantity and the gel fraction of adhesive phase 14, as adhesive phase formation compositions, it is preferable that containing active energy ray-curable compound. As active energy ray-curable compound, it is possible to enumerate such as: multifunctional (methyl) acrylic ester monomer less than 1000 of molecular weight, acrylate quasi-oligomer and imported the adduction acrylic polymer etc. of the group with (methyl) acryloyl group at side chain.
As multifunctional (methyl) acrylic ester monomer less than 1000 of molecular weight, it is possible to enumerate such as: BDO two (methyl) acrylate, 1,6-HD (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Polyethylene Glycol two (methyl) acrylate, neopentyl glycol adipic acid two (methyl) acrylate, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, bicyclopentyl two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) acrylate, 2 functional-type such as two (acryloyl-oxyethyl) isocyanuric acid esters and allylation cyclohexyl two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, dipentaerythritol three (methyl) acrylate, propanoic acid modifiies dipentaerythritol three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, 3 functional-type such as epoxy pronane modification trimethylolpropane tris (methyl) acrylate and three (acryloyl-oxyethyl) isocyanuric acid ester, 4 functional-type such as two glycerol four (methyl) acrylate and tetramethylolmethane four (methyl) acrylate, 5 functional-type such as modified dipentaerythritol five (methyl) acrylate of propanoic acid, 6 functional-type etc. such as dipentaerythritol six (methyl) acrylate and caprolactone modification dipentaerythritol six (methyl) acrylate. these multifunctional (methyl) acrylic ester monomers can be used alone one, it is also possible to combination uses two or more.
As multifunctional (methyl) acrylic ester monomer, it is preferable that framing structure has the monomer of circulus. Circulus can be carbocyclic ring structure, it is also possible to be heterocycle structure, furthermore it is possible to be single ring architecture, it is also possible to be multiring structure. As such multifunctional (methyl) acrylic ester monomer, it is possible to enumerate such as: two (acryloyl-oxyethyl) isocyanuric acid esters and three (acryloyl-oxyethyl) isocyanuric acid ester etc. have the monomer of isocyanurate structure, dihydroxymethyl bicyclopentane diacrylate, ethylene-oxide-modified hexahydro-phthalic acid diacrylate, Tricyclodecane Dimethanol acrylate, neopentyl glycol modified trimethylolpropane diacrylate and diamantane (obsolete) diacrylate etc.
As acrylate quasi-oligomer, it is preferable that weight average molecular weight is less than 50000. As such acrylate quasi-oligomer, it is possible to enumerate such as: polyester acrylate oligomer, Epoxy Acrylates oligomer, urethane acrylate quasi-oligomer, polyoxyalkylene acrylate oligoesters, PBAA oligoesters and silicone acrylates quasi-oligomer etc.
The hydroxy esterification of the polyester oligomer that two ends that polyester acrylate oligomer can obtain by such as making polybasic carboxylic acid and polyol condensating with (methyl) acrylic acid have hydroxyl obtains. It addition, polyester acrylate oligomer can also by making the terminal hydroxyl esterification of the oligomer obtained by epoxyalkane and polybasic carboxylic acid addition obtain with (methyl) acrylic acid.
Epoxy Acrylates oligomer can pass through such as to make (methyl) acrylic acid and the bisphenol-type epoxy resin of lower molecular weight, the oxirane ring of phenolic resin varnish type epoxy resin reacts carries out esterification and obtains. Alternatively, it is also possible to use partially modified for this Epoxy Acrylates oligomer dibasic acid anhydride and that obtain carboxy-modified type epoxy acrylate oligomer. Urethane acrylate quasi-oligomer can by such as making to be esterified by the urethane oligomer being obtained by reacting of polyether polyol, PEPA and polyisocyanates to obtain with (methyl) acrylic acid, and acrylic polyol quasi-oligomer can by making the hydroxy esterification of polyether polyol obtain with (methyl) acrylic acid.
For the weight average molecular weight of acrylate quasi-oligomer, the value of the standard that the is converted into polymethyl methacrylate preferably obtained by GPC method mensuration is less than 50000, it is more preferably more than 500 and less than 50000, more preferably more than 3000 and less than 40000. These acrylic compounds oligomer can be used alone one, it is also possible to combination uses two or more.
The adduction acrylic polymer having imported the group with (methyl) acryloyl group at side chain can be obtained by following manner: uses the copolymer of the monomer in above-mentioned (methyl) acrylate and molecule with cross-linking functional group, obtains by making a part of cross-linking functional group of the compound and copolymer with the group reacted with (methyl) acryloyl group and cross-linking functional group react. The weight average molecular weight of adduction acrylic polymer is generally more than 500,000 and less than 2,000,000 with the Molecular weights being converted into polystyrene.
< Photoepolymerizationinitiater initiater >
As adhesive phase formation compositions, when using energy ray-curable compound, from the viewpoint of improve elastic modelling quantity and the gel fraction of adhesive phase 14, use the compositions containing Photoepolymerizationinitiater initiater. as Photoepolymerizationinitiater initiater, it is possible to enumerate such as: benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin n-butylether, benzoin isobutyl ether, 1-Phenylethanone., dimethylamino benzoylformaldoxime, 2,2-methoxyl group-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinopropane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2-(hydroxyl-2-propyl group) ketone, benzophenone, to phenyl benzophenone, 4,4 '-diethylamino benzophenone, dichloro benzophenone, 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tert-butyl group anthraquinone, 2-amino anthraquinones, 2-methyl thiaxanthone, 2-ethyl thiaxanthone, CTX, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzil dimethyl ketal, 1-Phenylethanone. dimethyl ketal, ESCAROL 507 ester, oligomeric [2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone], 2,4,6-trimethyl benzoyl diphenyl base phosphine oxide etc. these compounds can be used alone one, it is also possible to combination uses two or more.
Relative to energy ray-curable compound 100 mass parts, the use level of Photoepolymerizationinitiater initiater is preferably below more than 0.2 mass parts and 20 mass parts.
< cross-linking agent >
From the viewpoint of improve elastic modelling quantity and the gel fraction of adhesive phase 14, adhesive phase formation compositions preferably comprises cross-linking agent (firming agent). As cross-linking agent, it is preferred to selected from polyfunctional isocyanate compound such as multifunctional amino-compound and polyisocyanate compound, multi-functional epoxy compound, multifunctional nitrogen heterocycle propane compound, multifunctionalAt least one in isoxazoline compound and multifunctional metallic compound. As cross-linking agent, for instance the cross-linking agent making binding agent cross-link by reacting and obtain can be used with the reactive functional groups of acrylic polymer. It addition, as adhesive phase formation compositions, it is possible to use containing the compositions of curing accelerator, cure retarder etc.
Object lesson as polyfunctional isocyanate compound, can enumerate such as: 2,4-toluene di-isocyanate(TDI), 2,6-toluene di-isocyanate(TDI), 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenyl methane-4,4 '-diisocyanate, diphenyl methane-2,4 '-diisocyanate, 3-MDPM diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride-4,4 '-diisocyanate, dicyclohexyl methyl hydride-2,4 '-diisocyanate and lysinediisocyanate etc. Alternatively, it is also possible to use the terminal isocyanate polyurethane prepolymer etc. that the trimer of these polyfunctional isocyanate compound and these polyfunctional isocyanate compound are reacted with polyol compound and obtained.
As the object lesson of multi-functional epoxy compound, can enumerate 1,3-double; two (N, N-diglycidyl amino methyl) benzene, 1,3-double; two (N, N-diglycidyl amino methyl) toluene, N, N, N ', N '-four glycidyl group-4,4-diaminodiphenyl-methane etc.
Object lesson as multifunctional nitrogen heterocycle propane compound, N can be enumerated, N '-diphenyl methane-4,4 '-bis-(1-azacyclopropane Methanamide) trimethylolpropane tris-��-aziridinyl propionic esters, tetramethylol methane three-��-aziridinyl propionic ester, N, N '-Toluene-2,4-diisocyanate, double; two (1-azacyclopropane Methanamide) triethylenemelanin of 4-etc.
As multifunctionalThe object lesson of isoxazoline compound, can enumerate 2-isopropenyl-2-Azoles quinolines etc. have the addition polymerization 2-of the substituent group with unsaturated carbon-carbon bond in the position of 2 carbonThe copolymer etc. that azoles quinoline is formed with other unsaturated monomer.
As the object lesson of multifunctional metallic compound, the coordination compound etc. of the polyvalent metals such as aluminium chelate compound compounds such as tri ethylacetoacetate aluminum, ethyl acetoacetate diisopropoxy aluminum, praseodynium aluminum can be enumerated. Wherein, from the viewpoint of obtain enough bonding forces, it is preferable that aluminium chelate compound compounds.
In adhesive phase formation compositions, it is possible to be used alone a kind of cross-linking agent, it is also possible to combination uses multiple different cross-linking agent. In order to improve the thermostability of adhesive phase, it is preferable that combine different cross-linking agent. Object lesson as the situation combining different cross-linking agent, it is preferable that the combination of polyfunctional isocyanate compound and the combination of multi-functional epoxy compound, polyfunctional isocyanate compound and multifunctional metallic compound.
From the viewpoint of bond properties and the adhesive phase of cohesiveness excellence can be formed, relative to acrylic polymer 100 mass parts, the use level of cross-linking agent preferably each cross-linking agent is more than 0.1 mass parts, it is more preferably more than 1 mass parts, and it is preferably below 30 mass parts, more preferably below 20 mass parts.
< silane coupler >
As adhesive phase formation compositions, it is possible to use the compositions containing silane coupler as required. By containing silane coupler, for instance when nesa coating fits in glass substrate etc., make the adaptation between adhesive phase and glass unit become good. As silane coupler, it is preferable that the compatibility with adhesive ingredients is good and has the organo-silicon compound at least in the molecule of transmitance with 1 alkoxysilyl.
As silane coupler, can enumerate such as: vinyltrimethoxy silane, VTES, the silicon compound containing polymerism unsaturated group such as methacryloxypropyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 2-(3, 4-expoxycyclohexyl) ethyl trimethoxy silane etc. has the silicon compound of epoxy construction, 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, the silicon compound containing amino such as N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-r-chloropropyl trimethoxyl silane etc. these compounds can be used alone one, it is also possible to combination uses two or more.
Relative to solid constituent 100 mass parts of cohesive layer formation compositions, the use level of silane coupler is preferably below more than 0.001 mass parts and 10 mass parts, more preferably more than 0.005 mass parts and below 5 mass parts.
< tackifying resin >
As adhesive phase formation compositions, it is possible to use containing the compositions of the tackifying resin regulating viscosity, bonding force and retentivity. As tackifying resin, it is possible to enumerate: the coal measures tackifying resins such as rosin based tackifying resin, terpenes tackifying resin, petroleum tackifying resin, coumarone-indenes resinoid, phenolic resin, xylene resin, styrene resin and other tackifying resin etc. As rosin based tackifying resin, it is possible to enumerate: the pentaerythritol ester etc. of resin, toll oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, newtrex, the glyceride of modified rosin and modified rosin. As terpenes tackifying resin, it is possible to enumerate: �� pinene resin, nopinene resin, cinene resin, aromatic modified terpene resin and terpene phenolic resin etc. As petroleum tackifying resin, it is possible to enumerate: C5 through-stone oleoresin, C9 through-stone oleoresin, C5 system/C9 system Copolymer Petropols, hydrogenation C5 through-stone oleoresin, hydrogenation C9 through-stone oleoresin, hydrogenation C5 system/C9 system Copolymer Petropols, bicyclopentadiene class Petropols and phenylethylene Petropols etc. These tackifying resins may be used alone, can also be used in combination two or more. Wherein, from the viewpoint of high with the compatibility of acrylic compounds triblock copolymer and show stable bonding force, it is preferred to use the tackifying resins such as styrene resin such as Petropols, alpha-methyl styrene polymer and styrene/��-methylstyrenecopolymer such as the rosin based resins such as the terpenoid resins such as hydrogenated terpene resin and terpenes phenolic aldehyde, hydrogenated wood rosin glycerol ester, disproportionated rosin ester and newtrex, C5/C9 through-stone oleoresin and fragrant same clan Petropols. These resins may be used alone, can also be used in combination two or more. In order to show high bonding force, it is preferable that the softening point of tackifying resin is more than 50 DEG C and less than 150 DEG C.
From the viewpoint of improve the bonding force of adhesive phase 14, relative to aforesaid propylene acids polymers 100 mass parts, the use level of the tackifying resin in adhesive phase formation compositions is preferably below more than 0.5 mass parts and 100 mass parts, more preferably more than 1 mass parts and below 50 mass parts.
< UV absorbent >
As adhesive phase formation compositions, it is preferable that containing UV absorbent. By containing UV absorbent, it is possible to protect the pigment used in the tone adjustment etc. of thermostability bonding sheet 1 by ultraviolet destruction.
As UV absorbent, it is possible to enumerate such as: benzophenone compound, benzotriazole compound and compound in triazine class etc. These UV absorbent can be used alone one, it is also possible to combination uses two or more.
< antirust agent >
As adhesive phase formation compositions, it is preferred to use containing the compositions of antirust agent. By containing antirust agent, when the adhesive phase 14 obtained contacts with metal electrode etc., it is possible to reduce the change of the absorbance caused by metal with the interaction of additive and the interaction etc. of metal and binding agent.
As antirust agent, can enumerate such as: there are the azole compounds of hydroxyl, triazole class compounds, benzotriazole compound, thiazole compound, benzothiazole compound, glyoxaline compound, benzimidazoles compound, phosphorus species, aminated compounds, nitrite compounds, surfactant-based, silane coupler class etc., wherein, from the viewpoint of prevent corrosive nature, it is preferable that the antirust agent of benzotriazole. It should be noted that antirust agent can be used alone one, it is also possible to combination uses two or more.
Antirust agent as benzotriazole, can enumerate such as: 1H-benzotriazole, methylbenzotrazole, 1-[N, double; two (2-ethylhexyl) amino methyl of N-] benzotriazole and 1-[double; two (2-ethylhexyl) amino methyl of N, N-] methylbenzotrazole etc.
Consider from the viewpoint and fusible viewpoint that obtain the above-mentioned effect as antirust agent, gross mass relative to the solid constituent of adhesive phase formation compositions, the use level of the antirust agent in adhesive phase formation compositions is preferably more than 0.1 mass % and below 5 mass %, more preferably more than 0.3 mass % and below 2 mass %.
As long as the thickness of adhesive phase 14 is in the scope playing effect of the present invention, it is not particularly limited, such as it is preferably more than 3 ��m, it is more preferably more than 10 ��m, more preferably more than 20 ��m, and it is preferably less than 500 ��m, more preferably less than 400 ��m, more preferably less than 300 ��m.
It addition, when adhesive phase 14 is made up of the 1st adhesive phase the 142, the 2nd adhesive phase 143 and core 141, the thickness of core 141 is preferably more than 2 ��m, more preferably more than 5 ��m, and it is preferably less than 50 ��m, more preferably less than 45 ��m. The thickness of the 1st adhesive phase the 142 and the 2nd adhesive phase 143 preferably respectively more than 1 ��m, and it is preferably less than 50 ��m.
(base material film 21)
As base material film 21, it is possible to suitably select the film with thermostability to use from plastic foil. as such plastic foil, can use such as: polyethylene terephthalate (PET), polybutylene terephthalate (PBT), the polyester films such as PEN (PEN), polyethylene film, polypropylene screen, cellophane, cellulose diacetate film, tri cellulose acetate membrane, cellulose acetate-butyrate film, polychloroethylene film, polyvinylidene chlorida film, polyvinyl alcohol film, vinyl-vinyl acetate copolymer film, polystyrene film, polycarbonate membrane, polymethylpentene film, polysulfone membrane, polyether-ether-ketone film, poly (ether sulfone) film, polyetherimde films, polyimide film, fluororesin film, polyamide membrane, acrylic resin film, norbornene resin film, and the plastic foil such as cycloolefin resin film. in the middle of these, from the viewpoint of be suitable as viewpoint and the transparency excellence that optical substrate uses, it is preferable that polyester film, polycarbonate membrane, polyimide film, norbornene resin film and cycloolefin resin film etc., more preferably polyester film.
For base material film 21, it is possible to the surface configuration at above-mentioned plastic foil adds the layer of various function. For base material film 21, for instance can have for closely sealed easy adhesive linkage firm in each layer on the face of the side that connects with functional layer 22 or adhesive phase 14, it is also possible on the face of the side that connects with functional layer 22, hard conating is set.
Thickness as base material film 21, it is preferred to more than 25 ��m, more preferably more than 30 ��m, more preferably more than 35 ��m, and it is preferably less than 250 ��m, more preferably and less than 225 ��m, more preferably less than 200 ��m. If it is considered that case above, then the thickness of base material film 21 is preferably more than 25 ��m and less than 250 ��m, more preferably more than 30 ��m and less than 225 ��m, more preferably more than 35 ��m and less than 200 ��m.
It should be noted that base material film 21 is expressed as simple layer in FIG, but base material film 21 is not limited to be made up of simple layer. Base material film 21 such as can be made up of 2 tunics of base material film Yu peeling agent layer lamination, it is also possible to is made up of 3 tunics in the same manner as stripping film 10.
< oligomer sealing >
For only carrying out ocular estimate by perusal in the prior art, oligomer precipitation being evaluated, the present inventor etc. is conceived to can the degree that oligomer precipitates out be evaluated quantitatively by measuring the haze value of thermostability bonding sheet. And, the present inventor etc. finds: by measuring the haze value of thermostability bonding sheet, oligomer precipitation is carried out quantitative assessment, it is possible to be effectively prevented the damage of transparent electrode layer, foreign body is mixed into.
In the thermostability bonding sheet 1 of present embodiment, precipitate out the oligomer on stripping film 10 top layer and make peeling base 11 (polyester film) obscure, make the haze value of stripping film 10 change. Therefore, in the present embodiment, it is measured by the absolute value of difference of haze value, i.e. �� haze value after the heating after the initial haze value of stripping film 10 and this stripping film 10 are heated 2 hours at 150 DEG C, it is possible to confirm the oligomer sealing in resin bed 12. But, in order to get rid of the impact of (during annealing) removed base material film 21 when heating uses, after initial haze value and heating, measuring of haze value is being removed base material film 21, is being measured with the state of stripping film 10 with the laminated body of adhesive phase 14.
In the present embodiment, owing to using above-mentioned resin bed formation compositions to form resin bed 12, and make the composition of (A)��(C) composition in appropriateness scope to prevent oligomer from precipitating out from peeling base 10, therefore, it is possible to making �� haze value is less than 0.15%. It should be noted that the initial haze value of thermostability bonding sheet 1 refers to the haze value before being heated 2 hours at 150 DEG C by thermostability bonding sheet 1. �� haze value is preferably less than 0.1%, more preferably less than 0.08%, and more preferably less than 0.04%.
It should be noted that in the present embodiment, �� haze value can as follows calculate. First, use mist degree instrument (trade name: NDH-2000, electricity Se Industrial Co., Ltd of Japan manufactures), measure the initial haze value (%) (meansigma methods of N=5) of thermostability bonding sheet 1 according to JISK7105. Then, thermostability bonding sheet 1 is hung in the drying machine of 150 DEG C and heat 2 hours, then according to JISK7105 measures the haze value (%) (meansigma methods of N=5) after heating. Then, the haze value after heating is deducted the absolute value of the value after initial haze value as �� haze value.
< purposes >
The thermostability bonding sheet 1 of present embodiment such as can use as the raw material film being used for nesa coating and glass substrate etc. are fitted in the touch panel manufacturing process of electrostatic capacity type. When thermostability bonding sheet 1 being used for the manufacture of nesa coating, by transparent conductive material film forming such as Indium sesquioxide., zinc oxide, stannum oxide, indium-Xi composite oxides, stannum-antimony composite oxides, zinc-aluminium composite oxide and indium-zinc composite oxides on adhesive phase 14, it is provided as the transparency conducting layer of functional layer 22. From the viewpoint of become continuous print thin film and obtain the viewpoint of stable electric conductivity and obtain enough transparencys, the thickness of transparency conducting layer is preferably more than 4nm, it is more preferably more than 5nm, more preferably more than 10nm, and it is preferably below 800nm, it is more preferably below 500nm, it is particularly preferred to for below 100nm.
In the thermostability bonding sheet 1 of present embodiment, the initial stage haze value of stripping film 10 is with to heat the absolute value delta haze value of the difference of haze value after the heating after 2 hours at 150 DEG C be less than 0.15%, even if therefore when arranging transparency conducting layer and implementing annealing, it also is able to reduce the change of the haze value of the stripping film before and after annealing, it is possible to the thermostability bonding sheet 1 being provided with transparency conducting layer is directly implemented annealing when possessing adhesive phase 14. And, in the annealing operation of nesa coating, the stripping film 10 in thermostability bonding sheet 1 also acts as the effect of screening glass, and the precipitation that therefore can be preferred for oligomer becomes the annealing at the temperature of about 150 DEG C of problem. Additionally, for the thermostability bonding sheet 1 of present embodiment, even if ooze out at annealing, the oligomer that also is able in other heat treated suppress to contain in polyester film, the crystallization deriving from oligomer can be suppressed to precipitate out on resin bed 12 surface, therefore, it is possible to suppress being mixed into and the damage of transparent electrode layer of the small foreign body that derive from oligomer bad as touch panel. Even if it should be noted that the thermostability bonding sheet 1 of present embodiment also is able to be suitable in employing the purposes needing heat treated beyond the manufacturing process of touch panel of nesa coating.
As mentioned above, according to above-mentioned embodiment, owing to the initial stage haze value of stripping film 10 is with to heat the absolute value delta haze value of the difference of haze value after the heating after 2 hours at 150 DEG C be less than 0.15%, therefore, it is possible to the change of the haze value of stripping film 10 before and after reduction heat treated, it is possible to the thermostability bonding sheet 1 being provided with transparency conducting layer is directly implemented annealing when possessing adhesive phase 14. Owing to the stripping film 10 comprising peeling base 11, resin bed 12 and peeling agent layer 13 functional layer to being arranged on base material film 21 can be utilized (such as; transparency conducting layer 22) rear side be protected by, therefore can omit the operation of screening glass of the rear side installing and unloading defencive function layer when manufacturing functional membrane. Thereby, it is possible to realize being shortened by manufacturing process to reduce the thermostability bonding sheet of the manufacturing cost of functional membrane.
(manufacture method of functional membrane)
It follows that the manufacture method of the functional membrane of present embodiment is illustrated with reference to Fig. 4 A��Fig. 4 C. At this, as an example of functional membrane, the example manufacturing nesa coating is illustrated, but the present invention can be applicable to the manufacture of the various functional membranes beyond nesa coating.
As shown in Fig. 4 A��Fig. 4 C, the manufacture method of the functional membrane of present embodiment includes lamination procedure, film formation process and heat treatment step, described lamination procedure is the operation that resin bed 12, peeling base 11, peeling agent layer 13, adhesive phase 14 and base material film 21 lamination successively obtain laminated body 3, described film formation process is film forming conductive material arrange functional layer (such as on base material film 32, transparency conducting layer 22) and obtain the operation of thermostability bonding sheet 1, described heat treatment step is the operation being heated thermostability bonding sheet processing.
In lamination procedure, as shown in Figure 4 A, strangle rod coating method (Meyerbarcoat) etc. with wheat resin bed formation compositions to be coated on an interarea of peeling base 11 arranges resin bed 12, strangle rod coating method etc. with wheat to be coated on another interarea of peeling base 11 by peeling agent layer formation compositions and arrange peeling agent layer 13, thus obtaining stripping film 10 simultaneously. Then, as shown in Figure 4 B, coating adhesive layer formation compositions on peeling agent layer 13 and adhesive phase 14 is set, then base material film 21 is set on adhesive phase 14, thus forming laminated body 3.
Then, in film formation process, as shown in Figure 4 C, transparency conducting layer 22 (ITO: tin indium oxide tunicle) is set on base material film 21 by sputtering method, CVD, PVD etc. and obtains thermostability bonding sheet 1. It follows that in heat treatment step, carried out the crystallization of ITO by the annealing that thermostability bonding sheet 1 is heated, make low-resistance transparent electrode layer 22. Here; owing to being provided with stripping film 10 in the rear side of the outer surface of transparency conducting layer 22; it is annealed processing when therefore can protect the rear side of transparency conducting layer 22 at other screening glass of not fitting etc. such that it is able to realize reducing manufacturing cost because shortening manufacturing process.
Embodiment
Hereinafter, the embodiment that carries out based on the effect for the clear and definite present invention and the present invention is described in detail. It should be noted that the present invention is not by any restriction of following example and comparative example.
The calculating > of < �� haze value
The thermostability bonding sheet made in embodiment and comparative example is cut into 5cm respectively square as test film. From this test film, stripping film is peeled off, use mist degree instrument (trade name: NDH-2000, electricity Se Industrial Co., Ltd of Japan manufactures) according to JISK7105, the mist degree of this stripping film is measured (meansigma methods of N=5), as initial haze value (%). Additionally, with fixture, one jiao of each test film is fixed, hang on after heating 2 hours in the drying machine of 150 DEG C, from this test film, stripping film is peeled off, according to JISK7105, the mist degree of this stripping film is measured (meansigma methods of N=5), as the haze value (%) after heating.
Haze value after heating is deducted the absolute value of the value after initial haze value as �� haze value, evaluated by following standard. If it should be noted that �� haze value is less than 0.15%, then the amount that oligomer precipitates out from the polyester film used as peeling base is considerably less, it is possible to reduce the impact on operation thereafter.
Zero (well): less than 0.15%
�� (bad): more than 0.15%
(embodiment 1)
(preparation section of resin bed formation compositions)
By (A) bisphenol A type epoxy compound (trade name: EPICLONH-360, DIC company manufactures: solid component concentration 40 mass %, weight average molecular weight 25000) 100 mass parts, (B) petchem (trade name: VYLONGK680, Toyo Boseki K.K manufactures, number-average molecular weight 6000, glass transition temperature 10 DEG C) toluene solution (solid component concentration 30 mass %) 19.0 mass parts, and (C) HMMM (trade name: CYMEL303, solid component concentration 100 mass %, NihonCytecIndustriesLtd. manufacture) 11.4 mass parts mixing. with the mixed solvent of toluene/butanone (hereinafter also referred to " MEK ")=50 mass %/50 mass %, mixed liquor is diluted so that solid constituent is 3 mass %, and is stirred. then, add methanol solution (solid component concentration 50 mass %) 2.9 mass parts of (D) p-methyl benzenesulfonic acid, obtain resin bed formation compositions.
(manufacturing process of resin bed formation film)
Strangle rod coating method with wheat and the resin bed formation compositions obtained is evenly coated at biaxial tension polyethylene terephthalate film (trade name: the E5001 as base material film, Toyo Boseki K.K manufacture, thickness 75 ��m) a surface on. Then, the base material film being coated with resin formation compositions passed through the baking oven of 150 DEG C in 20 seconds, forms the resin bed that thickness is 150nm, obtains the polyester film being formed with resin bed.
(preparation section of peeling agent layer formation compositions)
Then, with the mixed solvent of toluene/MEK=50 mass %/50 mass % by addition reaction-type polyorganosiloxane resin (trade name: KS-774, Shin-Etsu Chemial Co., Ltd manufactures) 100 mass parts dilutions so that solid constituent is 1.5 mass %, and is stirred. Then, add platinum catalyst (trade name: PL-50T, Shin-Etsu Chemial Co., Ltd manufactures) 1 mass parts, obtain peeling agent layer formation compositions.
(manufacturing process of stripping film)
Then, with wheat strangle rod coating method peeling agent layer formation compositions is evenly coated at base material film with on the face of resin bed opposition side. Then, the base material film being coated with peeling agent layer formation compositions passed through the baking oven of 150 DEG C in 20 seconds, forms the peeling agent layer of thickness 150nm, obtains stripping film.
(preparation section of binding agent)
The adhesive composition that match ratio (solid constituent ratio) by with following binding agent 1 is constituted is dissolved in toluene and is prepared for coating liquid.
< binding agent coordinates 1 >
Acrylic copolymer (butyl acrylate 95 mass parts and the copolymer of copolymer 5 mass parts of acrylic acid 2-hydroxy methacrylate, weight average molecular weight (Mw) 800,000) 100 mass parts
Polyfunctional acrylic ester compound (three (acryloyl-oxyethyl) isocyanuric acid ester; Toagosei Co., Ltd's manufacture, trade name " ARONIXM-315 ") 15 mass parts
Photoepolymerizationinitiater initiater (the mixture of the mass ratio 1:1 of benzophenone and 1-hydroxycyclohexylphenylketone; The manufacture of CibaSpecialtyChemicals company, trade name " IRGACURE500 ") 1.5 mass parts
Cross-linking agent (trimethylolpropane modified toluene diisocyanate; Nippon Polyurethane Industry Co., Ltd.'s manufacture, trade name " CORONATEL ") 3 mass parts
Silane coupler (3-glycidoxypropyltrime,hoxysilane; Shin-Etsu Chemial Co., Ltd's manufacture, trade name " KBM-403 ") 0.2 mass parts
(manufacturing process of thermostability bonding sheet)
With scraper type coating machine, the coating liquid of preparation is coated in above-mentioned operation on the peel ply of ready stripping film, then dried 1 minute at 90 DEG C. Then, with annealing polyester film (trade name: MelinexSA, thickness 125 ��m, the TeijinDuPontFilms company manufacture) laminating as base material film. The thickness of dried adhesive phase is adjusted to 25 ��m. Then, base material film is fitted on stripping film, after 30 minutes from stripping film side with illumination 600mW/cm2, light quantity 150mJ/cm2The condition irradiation ultraviolet radiation (UV) of (using the Non-polarized lamp Hvalve that FUSION company manufactures), has made thermostability bonding sheet. The adhesive phase obtained storage modulus at 23 DEG C is 0.86MPa, and gel fraction is 93%.
(embodiment 2)
As resin bed formation compositions, except making (B) petchem be 22.22 mass parts, (C) HMMM be 20 mass parts, (D) p-methyl benzenesulfonic acid methanol solution be 3.3 mass parts except, it is operated similarly to Example 1, obtains thermostability bonding sheet.
(embodiment 3)
As resin bed formation compositions, except making (B) petchem be 44.4 mass parts, (C) HMMM be 13.3 mass parts, (D) p-methyl benzenesulfonic acid methanol solution be 3.3 mass parts except, it is operated similarly to Example 1, obtains thermostability bonding sheet.
(embodiment 4)
As resin bed formation compositions, except (A) bisphenol A type epoxy compound is changed to (trade name: EPICLONEXA-123, DIC company manufactures: solid component concentration 30%, weight average molecular weight 45000) 100 mass parts, make (B) petchem be 14.3 mass parts, except (C) HMMM is 8.6 mass parts, the methanol solution of (D) p-methyl benzenesulfonic acid (solid component concentration 50 mass %) is 2.1 mass parts, it is operated similarly to Example 1, obtains thermostability bonding sheet.
(embodiment 5)
As resin bed formation compositions, except (B) petchem is changed to the toluene solution (solid component concentration 30 mass %) of (trade name: VYLONGK810, Toyo Boseki K.K manufacture: number-average molecular weight 6000, glass transition temperature 46 DEG C), it is operated similarly to Example 1, obtains thermostability bonding sheet.
(embodiment 6)
Coordinate 2 except the cooperation of adhesive composition being changed to following binding agent, and at 120 DEG C, carry out 1 minute dried, and do not carry out, beyond ultraviolet radiation, being operated similarly to Example 1, made thermostability bonding sheet. Adhesive phase storage modulus at 23 DEG C is 0.61MPa, and gel fraction is 88%.
< binding agent coordinates 2 >
Acrylic copolymer (acryllic acid butyl ester 80 mass parts, methyl methacrylate 10 mass parts and 2-hydroxyethyl methacrylate 10 mass parts, weight average molecular weight (Mw) 800,000) 100 mass parts
Cross-linking agent 1 (toluene di-isocyanate(TDI) class (TDI class) cross-linking agent; Toyo Ink Co., Ltd.'s manufacture, trade name " OribainBHS8515 ") 2.6 mass parts
Cross-linking agent 2 (metallo-chelate class cross-linking agent; Soken Chemical & Engineering Co., Ltd.'s manufacture, trade name " M-5A ") 0.25 mass parts
(embodiment 7)
Except the cooperation of adhesive composition being changed to following binding agent and coordinates 3 and do not carry out ultraviolet radiation, it is operated similarly to Example 1, has made bonding sheet. Adhesive phase storage modulus at 23 DEG C is 0.58MPa, and gel fraction is 75%.
< binding agent coordinates 3 >
Acrylic copolymer (butyl acrylate 94.9 mass parts, acrylic acid 2-hydroxy methacrylate 5 mass parts and the copolymer of acrylic acid 0.1 mass parts, weight average molecular weight (Mw) 1,800,000) 100 mass parts
Cross-linking agent (trimethylolpropane modified toluene diisocyanate; Nippon Polyurethane Industry Co., Ltd.'s manufacture, trade name " CORONATEL ") 3 mass parts
(comparative example 1)
Except resin bed not being set on stripping film, it is operated similarly to Example 1, obtains bonding sheet.
(comparative example 2)
As by resin bed formation compositions, except not using (B) petchem, make (C) HMMM be 10 mass parts, except the methanol solution of (D) p-methyl benzenesulfonic acid is 2.5 mass parts, it is operated similarly to Example 1, obtains bonding sheet.
(comparative example 3)
As resin bed formation compositions, except making (B) petchem be 222.2 mass parts, (C) HMMM be 26.7 mass parts, (D) p-methyl benzenesulfonic acid methanol solution be 6.7 mass parts except, it is operated similarly to Example 1, obtains bonding sheet.
[table 1]
Initial haze (%) Mist degree (%) after heat treatment �� mist degree (%) Oligomer sealing
Embodiment 1 1.51 1.53 0.02 ��
Embodiment 2 1.55 1.58 0.03 ��
Embodiment 3 1.55 1.57 0.02 ��
Embodiment 4 1.53 1.56 0.03 ��
Embodiment 5 1.55 1.59 0.04 ��
Embodiment 6 1.51 1.53 0.02 ��
Embodiment 7 1.51 1.53 0.02 ��
Comparative example 1 1.72 8.24 6.52 ��
Comparative example 2 1.54 1.95 0.41 ��
Comparative example 3 1.58 1.90 0.32 ��
As shown in Table 1, the variation delta mist degree of the bonding sheet of embodiment 1��embodiment 7 mist degree after the heat treatment is minimum, and oligomer composition does not precipitate out the outside to stripping film, and oligomer sealing is good. Therefore; for the bonding sheet of embodiment 1��embodiment 7; even if owing to carrying out heat treatment; oligomer is without precipitating out the outside to stripping film; even if therefore batching bonding sheet without functional layer being caused the infringement caused by oligomer, it is possible to do not use the oligomer sealing protecting film of high price to carry out heat treatment.
On the other hand, it is known that for the comparative example 1 being not provided with resin bed, �� mist degree is very big, has substantial amounts of oligomer to precipitate out, and oligomer sealing is substantially poor. Even if it addition, when being provided with resin bed, for the comparative example 3 that the content of the comparative example 2 not coordinating petchem and petchem is higher, �� mist degree increases, and oligomer sealing is not enough. Thus, for the bonding sheet of comparative example 1��comparative example 3, when batching bonding sheet after being annealed the heat treated such as process, the oligomer composition precipitated out due to heat treated to stripping film transfers to the surface of functional layer side, becomes the reason of the electrical characteristics of functional layer, optical characteristics variation.

Claims (10)

1. a thermostability bonding sheet, it possesses stripping film, adhesive phase and base material film,
Described stripping film comprises the peeling base formed by polyester film, be arranged on an interarea of described peeling base resin bed and be arranged at the peeling agent layer on another interarea of described peeling base,
Described adhesive phase is arranged on described peeling agent layer,
Described base material film is arranged on described adhesive phase,
Wherein, the initial stage haze value of described stripping film is with to heat the absolute value delta haze value of the difference of haze value after the heating after 2 hours at 150 DEG C be less than 0.15%.
2. thermostability bonding sheet according to claim 1, wherein, described peeling agent layer is formed by the solidification of addition reaction-type polysiloxanes.
3. thermostability bonding sheet according to claim 1, wherein, described resin bed is formed to solidify by compositions by the resin bed containing (A) bisphenol A type epoxy compound, (B) petchem and (C) multifunctional amino-compound and forms.
4. thermostability bonding sheet according to claim 3, wherein, in described resin bed formation compositions, the content of described bisphenol A type epoxy compound is the content of more than 50 mass % and below 80 mass %, described petchem be the content of more than 5 mass % and below 30 mass %, described multifunctional amino-compound is more than 10 mass % and below 40 mass %.
5. thermostability bonding sheet according to claim 3, wherein, the weight average molecular weight of described bisphenol A type epoxy compound is more than 10000 and less than 50000.
6. thermostability bonding sheet according to claim 3, wherein, the glass transition temperature (Tg) of described petchem is more than 0 DEG C and less than 50 DEG C.
7. thermostability bonding sheet according to claim 1, wherein, described resin bed is that the coating layer being coated on described base material film to be formed the solution of described resin bed formation compositions is heated and the cured film that formed.
8. thermostability bonding sheet according to claim 1, wherein, the thickness of described resin bed is more than 50nm and below 500nm.
9. a manufacture method for functional membrane, the method includes lamination procedure, film formation process and heat treatment step,
Described lamination procedure includes: adhesive phase and described base material film described in lamination successively comprising the peeling base formed by polyester film, on the described peeling agent layer of the stripping film of the resin bed that is arranged on an interarea of described peeling base and the peeling agent layer that is arranged on another interarea of described peeling base, thus the thermostability bonding sheet that absolute value delta haze value is less than 0.15% of the difference of haze value after heating after obtaining the initial haze value of described stripping film and heating 2 hours at 150 DEG C
Described film formation process includes: using conductive material film forming as functional layer on the described base material film of described thermostability bonding sheet,
Described heat treatment step includes: to film forming, the described thermostability bonding sheet of described functional layer is heated processing.
10. the manufacture method of functional membrane according to claim 9, wherein, described functional layer is transparency conducting layer.
CN201510810393.7A 2014-11-20 2015-11-20 The manufacturing method of heat resistance bonding sheet and functional membrane Active CN105619979B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-235770 2014-11-20
JP2014235770A JP6424070B2 (en) 2014-11-20 2014-11-20 Heat-resistant adhesive sheet and method for producing functional film

Publications (2)

Publication Number Publication Date
CN105619979A true CN105619979A (en) 2016-06-01
CN105619979B CN105619979B (en) 2019-11-12

Family

ID=56035489

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510810393.7A Active CN105619979B (en) 2014-11-20 2015-11-20 The manufacturing method of heat resistance bonding sheet and functional membrane

Country Status (4)

Country Link
JP (1) JP6424070B2 (en)
KR (1) KR102368739B1 (en)
CN (1) CN105619979B (en)
TW (1) TWI671381B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109313962A (en) * 2016-06-10 2019-02-05 日东电工株式会社 Transparent conducting film and touch panel
CN110885663A (en) * 2019-11-26 2020-03-17 塔威新材料科技(上海)有限公司 UV (ultraviolet) moisture dual-curing reaction type polyurethane hot melt adhesive composition
CN113226749A (en) * 2018-12-27 2021-08-06 日东电工株式会社 Protective sheet

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101993352B1 (en) * 2015-12-09 2019-06-26 주식회사 엘지화학 Light absorption film and polarizer plate comprising the same
KR101852837B1 (en) * 2016-07-21 2018-04-27 주식회사 오킨스전자 Method for manufacturing carrier for testing semiconductor package
JP7100541B2 (en) * 2018-08-29 2022-07-13 日本カーバイド工業株式会社 Laminate manufacturing method and laminate
JPWO2020196222A1 (en) * 2019-03-26 2020-10-01
KR102562078B1 (en) * 2020-01-10 2023-09-01 이솔화학 주식회사 Method for producing transparent film laminate
CN113999639A (en) * 2021-11-17 2022-02-01 九江福莱克斯有限公司 High-transparency temperature-resistant yellowing-resistant polyester adhesive and flexible covering film prepared from same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101622680A (en) * 2007-03-02 2010-01-06 日东电工株式会社 Transparent conductive film with adhesive layer, and its forming method
JP2013060555A (en) * 2011-09-14 2013-04-04 Lintec Corp Mold release film and method for producing the same
CN104073180A (en) * 2013-03-28 2014-10-01 琳得科株式会社 Adhesive sheet
CN104231959A (en) * 2013-06-10 2014-12-24 日东电工株式会社 Separator-attached adhesive layer, method for producing the same and adhesive layer-attached optical film with separator

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS548121Y2 (en) * 1974-08-28 1979-04-14
JP4151821B2 (en) 2002-01-11 2008-09-17 日東電工株式会社 Surface protective film for transparent conductive film and transparent conductive film
JP5612388B2 (en) * 2010-07-30 2014-10-22 日東電工株式会社 Adhesive layer for transparent conductive film, transparent conductive film with adhesive layer, transparent conductive laminate, and touch panel
JP5877122B2 (en) * 2012-05-21 2016-03-02 藤森工業株式会社 Surface treatment film, surface protection film, and precision electrical and electronic parts on which it is bonded

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101622680A (en) * 2007-03-02 2010-01-06 日东电工株式会社 Transparent conductive film with adhesive layer, and its forming method
JP2013060555A (en) * 2011-09-14 2013-04-04 Lintec Corp Mold release film and method for producing the same
CN104073180A (en) * 2013-03-28 2014-10-01 琳得科株式会社 Adhesive sheet
CN104231959A (en) * 2013-06-10 2014-12-24 日东电工株式会社 Separator-attached adhesive layer, method for producing the same and adhesive layer-attached optical film with separator

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109313962A (en) * 2016-06-10 2019-02-05 日东电工株式会社 Transparent conducting film and touch panel
CN113226749A (en) * 2018-12-27 2021-08-06 日东电工株式会社 Protective sheet
CN110885663A (en) * 2019-11-26 2020-03-17 塔威新材料科技(上海)有限公司 UV (ultraviolet) moisture dual-curing reaction type polyurethane hot melt adhesive composition

Also Published As

Publication number Publication date
JP6424070B2 (en) 2018-11-14
JP2016098297A (en) 2016-05-30
CN105619979B (en) 2019-11-12
KR102368739B1 (en) 2022-02-28
KR20160060595A (en) 2016-05-30
TWI671381B (en) 2019-09-11
TW201627443A (en) 2016-08-01

Similar Documents

Publication Publication Date Title
CN105619979A (en) Method for manufacturing heat resistance adhesive sheet and function film
CN101802122B (en) Adhesive sheet, upper electrode for touch panel, and image display device
CN103660513B (en) The manufacture method of duplexer and duplexer
CN102702988B (en) Method for manufacturing adhesive composition, adhesive composition and adhesive tape
CN104972779A (en) Non-substrate type adhesive tape for transper printing and preparation method thereof
CN102165558A (en) Method for concave and convex pattern formation and apparatus for manufacturing concave and convex pattern
CN102272887A (en) Photocurable transfer sheet, and method for forming uneven pattern using same
CN107004383A (en) Surface protection panel double-faced pressure-sensitive adhesive sheet and surface protection panel
CN104073180A (en) Adhesive sheet
CN102762371A (en) Hard coat film and process for producing same
JP6810123B2 (en) Adhesive sheet, display body and manufacturing method of display body
CN111748289A (en) Colored adhesive sheet and display
KR20150087218A (en) Substrate-less double-sided adhesive sheet
CN104946148B (en) Bonding sheet
KR101614076B1 (en) Re-release acrylic adhesive and release agent
CN107001890A (en) Adherence composition, sticker and adhesive sheet
KR100744685B1 (en) Uv ray curable adhesive sheat and use thereof
KR20210114854A (en) Adhesive scattering prevention sheet and display
TW202126487A (en) Transfer film, manufacturing method of laminate
TWI732861B (en) Adhesive sheet on both sides without substrate
CN113165356B (en) Multilayer sheet and transfer material
KR102139070B1 (en) Decoration film suitable for small lots and multi items
JP7426539B2 (en) Method of manufacturing the construct
JP2018144381A (en) Coating film and adhesive sheet laminate
KR102547339B1 (en) Anti-scattering film, and electronic display and electronic device including the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant